Nickel oxide and alkali hydride catalyst for ethylene polymerization



United States Patent Ofiice 2,717,388 Far-tented Sept. 13, 1955 NICKEL OXIDE AND ALKALI HYDRIDE CATA! LYST FOR ETHYLENE POLYMERIZATION Morris Feller, Park Forest, and Edmund Field, Chicago, 111., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Application July 8, 1954, Serial No. 442,202

12 Claims. (Cl. 26094.9)

polymerization or interpolymerization of ethylene in substantial yields to form high molecular Weight normally solid polymeric materials having molecular weights ranging upwardly from 300. These and other objects of our invention will become apparent from the following description thereof.

Briefly, the inventive process comprises the conversion of ethylene in substantial yields to high molecular weight polymers having a molecular weight of at least 300 and including grease-like, wax-like and tough, resinous ethylene polymers, by contacting ethylene with a catalytic mixture prepared by admixing an alkali metal hydride with a solid catalyst comprising essentially a nickel oxideactivated carbon containing a minor proportion, usually between about 0.1 and about weight percent, of nickel oxide (calculated as nickel) and a major proportion of activated carbon, preferably a coconut charcoal. The catalyst will be hereinafter referred to as the nickel catalyst. The alkali metal hydrides have the formula MH wherein M is lithium, sodium, potassium, rubidium or cesium. We prefer to use the hydrides of lithium and sodium because they are commercially available and relatively cheap. The inclusion of the alkali metal hydride with the nickel catalyst results in substantially increased yields of solid polymers of ethylene.

The contacting of ethylene, nickel catalyst and alkali metal hydride is effected at temperatures within the range of about C. to about 250 C., preferably about 100 C. to about 150 C. It is highly desirable to supply to the reaction zone a liquid medium which serves both as a reaction medium and a solvent-for the solid reaction products. Suitable liquid reaction media for polymerization include various hydrocarbons, such as liquid saturated hydrocarbons or an aromatic hydrocarbon such as benzene, toluene or Xylenes. The conversion of ethylene or other feed stock can be effected'in' the absence of a liquid'reaction medium and the catalyst containing accumulated solid polymeric conversion products can be treated from time to time, within or outside'the conversion zone,to effect removal of conversion products therefrom and, if necessary, reactivation or regeneration of the catalyst for further use. The ethylene partial pres sure in the reaction zone can be varied betweenabout atmospheric pressure and 15,000 p. s. i. g. or even higher pressures, but is usually elfected at pressures between pore diameters of about 20 to 30 about 200 and about 5000 p. s. i., or most often at about 1000 p. s. i.

The practice of the process of the present invention leads to ethylene polymers of widely variant molecular Weight ranges and attendant physical and mechanical properties, dependent upon the selection of operating conditions. The inventive process is characterized by extreme flexibility both as regards operating conditions and as regards the products producible thereby. Thus the present process can be effected over extremely broad ranges of temperature and pressure. The practice of the present process can lead to greasedike ethylene homopolymers having an approximate molecular weight range of 300 to 700, wax-like ethylene homopolymers having an approximate specifice viscosity (X10 between about 1000 and 10,000, and tough, resinous ethylene homopolymers having an approximate specific viscosity (X10 of 10,000 to more than 300,000 [(1 relative1)( 10 By the term tough, resinous polyethylene as used herein, we mean polymer having a brittle point below -50 C. (A. S. T. M. Method D746-51T), impact strength greater than two foot pounds per inch of notch (A. S. T. M. Method D256-4'7T-lzod machine) and minimum elongation at room temperature (25 C.) of

Ethylene may be polymerized alone or in the presence ofpropylene or other mono-olefinic hydrocarbons such as n-butylenes, isobutylenes, t-butylethylene; acetylene, butadiene, isoprene, and the like, usually in proportions between about 1 and about 25% by weight, based on the weight of ethylene.

An effective proportion of alkali metal hydride promoter is employed in our process, e. g., from about 0.01 to about 1 part by weight per part by weight of nickel catalyst (total weight of solid catalyst) although the ratio may be 2 or even more. Usually, we employ about 0.1 to about 0.5 part by weight of alkali metal hydride per part by weight of the supported nickel catalyst. The optimum proportions can readily be determined in specific instances by simple small-scale tests with the specific feed stocks, liquid reaction medium, reaction medium: catalyst ratio, catalyst, temperature, pressure and nature of the product which is desired.

The nickel component of the catalyst is extended upon a major proportion of an activated carbon. Thus, we may employ activated charcoals derived from cellulosic materials, particularly coconut, having surface areas between about 700 and about 1200 square meters per gram, pore volumes of about 0.53 to 0.58 cc. per gram and A, and, in some instances, small amounts of combined oxygen. The activated charcoal or other carbon support may be pretreated with nitric acid before use as a catalyst support in order to remove basic materials, for example, as described in E. F. Peters application for United States Letters Patent, Serial No. 164,825, filed May 27, 1950. p

The preparation of nickel catalysts supported upon activated carbon, particularly coconut charcoal, is well known in the art and the preparative methods form no part of the present invention. Usually we prefer to prepare the catalyst by a cheap, simple and efiicacious technique, which is described briefly hereinafter.

A suitable method of catalyst preparation involves ad- 3 sorbing nickel nitrate from an aqueous solution upon a porous active carbon such as a suitable charcoal in an amount sufficient to produce the desired nickel content in the finished catalyst. The charcoal containing adsorbed nickel salt is then treated thermally at tempera tures between about 200 and about 350 C. to effect decomposition of nickel nitrate to form nickel oxide, suitably by heating under a partial vacuum such as l to 20 mm. of mercury (absolute pressure) or in the presence of steam or by the application of heat, vacuum and steam, as is known in the art. The resultant catalystcomprises principally nickel oxide extended upon charcoal.

Although the nickel catalyst may contain between about 0.1 and about 20 weight percent of nickel (calculated as metallic nickel), we usually employ catalyst containing between about 3 and about 10 weight percent of nickel.

The activated carbon support seems to play a unique role in the catalyst. Other supports which might be considered prima facie equivalents, greatly reduce or virtually destroy the power of the catalyst to produce solid polymers from ethylene, viz. alumina and silica supports such as kieselguhr, as will be 'brought'out in more detail hereinafter.

' If it is desired to employ the nickel catalyst in the form of pellets large enough to be retained on a 20-mesh sieve or at least about 0.1 inch in the largest dimension. it is' desirable to pellet the nickel catalyst with between about SOand about 95 weight percent, based on the total weight of the pellet, of a difficultly reducible metal oxide filler material such as alumina; titania,zirconia' or silica.

The nickel catalyst can be employed in various forms and sizes,e. g., as powder, granules, microspheres, broken filter cake, lumps, or shaped pellets. A convenient form in which thecatalysts may be employed is as granules of about 20400 mesh/ inch size range.

Reaction pressures may be varied within the range of about 15 p. s. i. ethylene partial pressure to the maximum ethylene partial pressure which can economicallybe employed in suitable commercial equipment, for example up to as'much as30,000 p.s.'i. A convenient ethylene partial "pressure range for the manufacture of solid polymers'by theuse of the present catalyst is about"200 to about 10,000 p. s i., which constitutesa distinct advan tage overthe commercial high'pressure ethylene polymerization processes which apparently require operating pressures in'the range of about 20,000 to about 50,000

p. s. 1. i

The charging stock to the present polymerization process preferably comprises essentiallyethylene1 The ethylene' charging stocks may contain inert hydrocarbons, as in refinery gas streams, for example,' methane, ethane; propane, etc. However, it is preferred to employ as pure and concentrated ethylene charging stocks as his possible to obtain. It is desirable to minimize or avoid the introduction of oxygen, carbondioxide, water or sulfur compounds into contact with the catalyst.

The contact time or space velocity employed in the polymerization process will be selected with reference to the other variables, catalysts, the specifictype ofprocluct desired and the extent of ethylene conversion desired in any given run or pass over the catalyst; 'Inge'neral, this variable is readily adjustable to obtain the desired results: In operations in" which the olefin charging stock is caused to flow continuously into and out of contact with the solid catalyst, suitable liquid hourlysp ace velocities are usually selected between about 0.1 and about 10 volumes, preferably about 0.5 to 5 or about 2 volumes of olefin solution in a liquid reaction medium, which is usually an aromatic hydrocarbon such as'benzene or xylenes; tetralin or other cycloaliphatic hydrocarbon, such as cyclohexane or decalin (decahydronaphthalei f l' The amount of ethylene in such solution may be in the range of about 2 to 50% by weight, preferably about 2 to about 10 weight percent or, for example, about 5 to 10 weight percent. When the etheyl ene concentration in the liquid reaction medium is decreased below about 2 weight percent, the molecular weight 'and melt viscosity of the polymericproducts tend to dropsharply. In gen- "eral, the rate of ethylene polymerization tends to increase with increasing concentration "of the ethylene'in the liquid reaction medium. However, the rate of ethylene polymerization to form high molecular weight, normally solid polymers is preferably not such as to yield said solid polymers in quantities which substantially exceed the solubility thereof in said liquid reaction medium under the reaction conditions, usually up to about 5-7 Weight percent, exclusive of the amounts of polymeric products which are selectively adsorbed by the catalyst. Although ethylene concentrations above 10 Weight percent in the liquid reaction medium may be used, solutions'of e'thylene polymer above 540% in the reaction medium become very viscous'and difiicult to handle and severe cracking or spalling of the catalyst particles or fragments may occur, resulting in catalyst carry-over as fines'with the solution of polymerization products and extensive loss of catalyst from the reactor.

In batch operations, operating periods between one-half and about 20 hours are employed and'the reaction autoclave is charged with ethylene as the pressure falls as a result of the olefin conversion reaction.

The olefin charging stocks can be polymerized in the gas phase and in the absence of a liquid reaction medium by contact with the catalyst. Upon completion of the desiredpolyrnerization reaction it is then possible to treat the catalyst for the recovery of the solid polymerization products, for example by extraction with suitable solvents. However, in the interests of obtaining increased rates of olefin conversion and of continuously removing solid conversion products from the catalyst, it is much preferred to effect the conversion of the olefin in the presence of suitable liquid reaction 'media. The liquid reaction medium may also be employed as a means of contacting the "olefin with catalyst by preparing a solution of the olefin feedstock in the liquid reaction medium and contacting the resultant solution with the polymerization catalyst. The liquid reaction medium functions as a solvent to remove some of the normally solid product from the catalyst surface. A Various classes of hydrocarbons or their mixtures which are liquid under the polymerization conditions of'the present process ca'n be employed. Members of the aromatic hydrocarbon series, particularly the mononuclear aromatic hydrocarbons, viz., benzene, toluene, xylenes, mesitylene and xylene p-cymene mixtures can be employed. Tetrahydronaphthalene can also be employed. In addition, we niay employ such aromatic hydrocarbons asethylbenzene, isopropylbenzene, sec-butylbenzene, t-butylbenze'ne, ethyltoluene, 'ethylxylenes, hemimellitene, pseudocumenegprehnitene, isodurene, diethylbenzenes, isoam'ylbenzene and the like. Suitable aromatic hydrocarbon fractions can be obtained by the selective extraction of aromatic naphtha's," from hydroforming operations as distillates-or-bottom s, from cycle stock fractions of crack ing operationsfetc. i

wen'i'ay also employ certain alkyl naphthalenes which are liquid under the polymerization reaction conditions, for example, 7 l-rnethylnaphthalene. '2-isopropylnaphthalen'ejl-n-arnylnaphthalene, and the like, or commercially produced fractions containing these hydrocarbons; Y

Certain classes of aliphatic hydrocarbons can also be employed as a liquid hydrocarbon reactionmedium'in the present process. Thus, we may employ various-saturated hydrocarbons (alkanes and cycloalkanes) which areliquidunder the polymerization reaction conditions and which do not crack substantially under'the reaction conditions; Either pure alkanes or cycloalkanes or commercially available mixtures, freed of catalyst poisons, may be employed. For example. we may employ straight run naphthas or kerosenes containing alkanes and cyclo'alkanes. Specifically, we may employ liquid or liquefied alkanes such as n-pentane, n-hexane, 2,3-dimethylbutane, rr-octane, iso-octane (2,2,4-trimethylpentane), n-decane, n-dodecane, cyclohexane, methylcyclohexane, dimethylcyclopentane, ethylcyclohexane, decalin, methyldecalins,

s iirsth s sss i s a th like- We may also employ a liquid hydrocarbon reaction medium comprising liquid olefins, e. g., n-hexenes, cyclohexene, octenes, hexadecenes and the like.

The normally solid polymerization products which are retained on the catalyst surface or grease-like ethylene polymers may themselves function to some extent as a liquefied hydrocarbon reaction medium, but it is highly desirable to add a viscosity-reducing hydrocarbon, such as those mentioned above, thereto in the reaction zone.

The liquid hydrocarbon reaction medium should be freed of poisons before use in the present invention by acid treatment, e. g., with anhydrous p-toluenesulfonic acid, sulfuric acid, or by equivalent treatments, for example with aluminum halides, or other Friedel-Crafts catalysts, maleic anhydride, calcium, calcium hydride, sodium or other alkali metals, alkali metal hydrides, lithium aluminum hydride, hydrogen and hydrogenation catalysts (hydrofining), filtration through a column of copper grains or 8th group metal, etc., or by combinations of such treatments.

We have purified C. P. xylenes by refluxing with a mixture of 8 weight percent M003 on A1203 catalyst and LiAlH4 (50 cc. xylene-1 g. catalyst-02 g. LiAlHi) at atmospheric pressure, followed by distillation of the xylenes. Still more effective purification of solvent can be achieved by heating it to about 225-250 C. with either sodium and hydrogen or NaH plus 8 weight percent Moos-A1203 catalyst in a pressure Vessel.

Temperature control during the course of the ethylene conversion process can be readily accomplished owing b to the presence in the reaction zone of a large liquid mass having relatively high heat capacity. The liquid hydrocarbon reaction medium can be cooled by heat exchange inside or outside the reaction zone.

When solvents such as xylenes are employed alkylation thereof by ethylene can occur under the reaction conditions. The alkylate is removed with grease in the present process, can be separated therefrom by fractional distillation and can, if desired, be returned to the polymerization zone.

The following specific examples are introduced in order to illustrate but not unduly to limit our invention. The exemplary operations were effected in 250 cc. capacity stainless steel pressure vessels provided with a magnetically-actuated stirring device which was reciprocated through the liquid in the vessel in order to obtain good contacting of the ethylene and catalyst components.

Example 1 The autoclave was charged with 100 cc. of dehydrated and decarbonated toluene which was freshly distilled, 0.25 g. of sodium hydride and 1 g. of nickel catalyst. This catalyst was prepared by evaporating a 10% nickel nitrate solution while stirring an activated coconut charcoal, 8-14 mesh per inch, until all the nickel nitrate was deposited on the support. The catalyst was dried at 110 C. and then heated in steam at atmospheric pressure while the temperature was gradually raised from 100 C. to 290 C. Decomposition of the nickel nitrate on the charcoal occurred to form a catalyst comprising essentially NiO on charcoal. The nickel catalyst contained weight percent of nickel. The contents of the autoclave were heated with stirring to 128 C. and ethylene was then injected to a partial pressure of 875 p. s. i. Reaction was continued for 20.5 hours. Upon conclusion of the reaction the reactor contents were cooled to room temperature, the pressure was vented to atmospheric pressure and the nickel catalyst containing adsorbed polyethylenes was removed and extracted with hot xylenes. The hot xylenes solution was cooled to room temperature to precipitate a tough, resinous ethylene polymer which was filtered and the filtrate was evaporated to leave a greaselike solid polyethylene residue. Excess sodium hydride was destroyed by alcohol addition. The reaction yielded 3.77 g. per g. of the nickel catalyst of a solid polymer of ethylene having a specific gravity (24/4 C.) of 0.947,

Cir

,6 Williams plasticity of 39.8 and melt viscosity of 2.3X10 (method of Dienes and Klemm, J. Appl. Phys. 17, 458-71 (1946)). The yield of solid grease-like polyethylenes was 1.57 g. per g. of the nickel catalyst.

In sharp'contrast to the above results are the results which were obtained in the following experiment in which no hydride promoter was employed. The charge to the reactor was the same as in the above example butno promoter was included and it was found that the yield of solid polyethylenes was only 0.01 g. per g. and the yield of solid grease-like polyethylenes was only 0.05 g. per g. of the solid catalyst. The reaction period was 20 hours.

In another control run the reactor was charged with cc. of the purified toluene, 2 g. of the 5% nickel oxidecharcoal catalyst, heated with stirring to 131 C. and then pressured with ethylene to a partial pressure of 910 p. s. i. The operating period was 20.5 hours. The reaction yielded only a trace of solid polyethylenes and 0.25 cc. of a liquid polymer per gram of the nickel catalyst.

Example 1 was repeated, except that the catalyst employed was a commercial preparation of 50% nickel on kieselguhr. Only traces of a polyethylene resin were produced and a wax-oil (grease) mixture in the-yield of about 2 g. per g. of nickel catalyst.

Example 2 The reactor was charged with 100 cc. of purified toluene, 0.25 g. of LiH and 1 g. of nickel catalyst having the same composition and prepared by the same method as the nickel catalyst of Example 1. The contents of the reactor were heated with stirring to 126 C. and ethylene was then introduced to a partial pressure of 860 p. s. i. Reaction was continued for 20 hours. The reaction products were worked up as in Example 1. The yield of solid, resinous polyethylenes was 4.2 g. per g. of nickel catalyst. The reaction also yielded 1.9 g. of solid grease-like polyethylenes per gram of the nickel catalyst. The resinous polymer had a density (24/4 C.) of 0.953, Williams plasticity of 33.2 and melt viscosity of l.2 l0".

In contrast were the results obtained in the following experiment. The reactor was charged with 100 ml. of thoroughly dried benzene, 0.61 g. of lithium hydride and 0.3 g. of commercial 50 weight percent nickel-on-kieselguhr catalyst. The reactor was flushed with ethylene and heated to 49 C. under an ethylene pressure of 850 p. s. i. for 3% hours. Only a trace of solid or grease-like polymer was produced. This experiment emphasizes the importance of the carbon support for nickel catalysts.

Example 3 The process of Example 2 is repeated but the LiH is replaced by 1.25 g. of KH. The products are worked up as before to produce solid polymers of ethylene.

In lieu of, or in addition to, the nickel catalysts, we may employ CoO-carbon catalysts, which can be prepared in about the same way as the nickel catalysts we have described.

In large scale operations, the flow-scheme shown in the E. Field and M. Feller application, Serial No. 324,608, filed December 6, 1952, may be employed.

The polymers produced by the process of this invention can be subjected to such after-treatment as may be desired, to fit them for particular uses or to impart desired properties. Thus, the polymers can be extruded, mechanically milled, filmed or cast, or converted to sponges or latices. Antioxidants, stabilizers, fillers, extenders, plasticizers, pigments, insecticides, fungicides, etc. can be incorporated in the polyethylenes and/or in by-product alkylates or greases. The polyethylenes may be employed as coating materials, binders, etc.

The polymers produced by the process of the present invention, especially the polymers having high specific viscosities, can be blended with the lower molecular weight polyethylenes to impart stiifness or flexibility or other desired properties thereto. The solid resinous products produced by the process of the present invention can, likewise; be blended inany desired proportions with hydrocarbon'oils, waxes-such as parafiin or petrolatumwaxes; with 'ester-'waxes,-with high molecular weight polybutylenes, and with other organic materials. Small'proportions betweenabout .lll'and' aboutl percent ofthe various polymers ofethylene produced by the-process of the present invention can'be dissolved or dispersed-in hydrocarbon lubricatingoils to increase V I. and to decrease oil consumption when the compounded oils are employed in motors; larger amounts oi polyethylenes may be compounded with oils of various kinds and for various purposes.

The products can be employed in small proportions to substantially increase the viscosity-of fluent liquid hydrocarbon oilsand as gelling-agentsfpr such oils. -Ihe polymers produced: by-the'--present process-can be subjected'to chemical-modifying-treatments, such as halogenation, halogenationfollowed by dehalogenation, sulfohalogenation by "treatment-with sulfuryl chloride or a mixture of sulfur dioxide and=chlorine,- sulfonation, and other reactions to which hydrocarbons may be'subjected.

Having thuswl'escribed our invention, what we-claim is: '1; In a processtorthe preparation of'a normally solid polymer, the steps-of contacting ethylene with acatalytic mixture prepared by admixing an alkali metal hydride with a catalyst comprising essentially nickeloxide in a proportion between abcutx'thland about 20 weight percent, calculated as elemental nickel, supported upon an acti'va'ted'carbon, 'eifec'tihg" said contacting at an effective polymerizationtemperature'between about'25f C; and smut-250%; and recovering a normally "solid polymer thus'producd. "22 lTn"a"process for the preparation of a normally solid polymer: thestepscf contacting ethylene with 'a'catalytic mixture prepared by admixing an alkali metal hydride With a catalyst"comprisin'g'essentially' nickel oxide in a p'roportion' b'etwen about'OLTandabout 20 weight percent,- calculated asele'riiental' nickel; su orteanpmr 'an activated carbon, effecting said contacting in the presence of a liquid hydrocarbon *reaction'medium at an effective polymerizationtemperature between about 2?: Q.-=and about 250 C., andtrecovering'a normally solid polymerthusproducedr 1 r r --3: 'l he process of claim 2 wherein said hydride is lithiumhydride.- 1 v 7' -'4. The process of claim 2 wherein said hydride is sodium hydride; I Y V I 5.---The process of claim 2 wherein said hydride is potassiumhydride.-

a 1@ -'6. A' process for the production of a normally solid polymer, which processcomprisescontacting-ethylene and a liquid hydrocarbon-reaction medium atan effective polymerizationtemperaturebetweenabout 25-" C; and about 250 C. with acatalyticmixture prepared by admixing an alkali metal hydride in a weight ratio between about l).()1 and about l-with a catalyst comprisingessentially-nickel oxide in a proportion between about-i-0al-=and' about 2Q weight percent, calculated as elemental nickel, supported upon an activated coconut charcoal and recovering -a normally solid polymer-thusproduced: 1 w

7. The process'of claim 6 wherein the polymerization temperature is between about 100 C andsabout ISO-" C:

8. The process of 'claim 6 wherein said liquid hydrocarbon reaction medium isamonocyclic aromatic hydrocarbon 1 .7 .3',i 9: The process of claim 6 wherein said liquid hydrocarbon reaction medium-is a saturated hydrocarbon. IOJThe-process-of cl'aim- 6-wherein said-hydride is lithiumhydride?.v V a, l1-'.- The process of claim 6 wherein said hydride is diu .hyd id a, 1. .c l. '--l-2.The-process of claim 6 wherein said hydride is potassiumhydride. 1

No references cited. 

1. IN A PROCESS FOR THE PREPARATION OF A NORMALLY SOLID POLYMER, THE STEPS OF CONTACTING ETHYLENE WITH A CATALYTIC MIXTURE PREPARED BY ADMIXING AN ALKALI METAL HYDRIDE WITH A CTALYST COMPRISING ESSENTIALLY NICKEL OXIDE IN A PROPORTION BETWEEN ABOUT 0.1 AND ABOUT 20 WEIGHT PERCENT, CALCULATED AS ELEMENTAL NICKEL, SUPPORTED UPON AN ACTIVATED CARBON, EFFECTING SAID CONTACTING AT AN EFFECTIVE POLYMERIZATION TEMPERATURE BETWEEN ABOUT 25* C. AND ABOUT 250* C., AND RECOVERING A NORMALLY SOLID POLYMER THUS PRODUCED. 